Polycyclic iminoisoindoline chelates

ABSTRACT

This invention relates to novel compounds of the isoindolenine series. More particularly, the present invention relates to certain novel 1-imino-3-(4-imino-5thiazolidinylidene)isoindolines, 1-imino-3-(4-imino-2-thiazolin5-ylidene)isoindolines, water-insoluble pigments prepared therefrom, and to methods for their preparation.

United States Patent 2 Crounse et al.

[ Nov. 11, 1975 POLYCYCLIC IMINOISOINDOLINE C HELATES Inventors: NathanN. Crounse; Nicholas A. Ambrosiano, both of Cincinnati, Ohio Assignee:Sterling Drug lnc., New York, NY.

Filed: Nov. 20, 1972 Appl. No.: 308,163

US. CL... 260/270 PD; 260/24l.1 L; 260/242; 260/293.6l; 260/299;260/306]; 260/326! lnt. Cl. C07D 417/14 Field of Search 260/270 R, 270P, 302 E, 260/299. 270 PD, 424/245 References Cited UNITED STATESPATENTS ll/l944 Calva 424/325 Primar xannnerPaul M. Coughlan. Jr.Assistant E\'aminerMark L. Berch Attorney, Agent, or Firm-Lynn T.Fletcher; B. Woodrow Wyatt 2 Claims, No Drawings cyclic ring having thesame orientation as a thiazole POLYCYCLIC IMINOISOINDOLINE CHELAT'ESring and selected from the group consisting of The invention describedherein relates to new and useful compounds classified in the art ofchemistry as 5 E l -imino-3-( 4-imino-5 -thiazolidinylidene)isoindolines and l-imino-3-(4-imino-Z-thiazolin-S-ylidene)isoindolines,to valuable metal chelate pigments derived thereand from and tointermediates and processes for obtaining them. N The invention soughtto be patented, in a first composition of matter aspect, resides in thenovel metal chelate pigments of the formula in which Z is NH, O or S,and N=B is lower-alkylamino,

4- l5 di-lower-alkylamino, piperidino, pyrrolidino, morpho- /N I lino,phenylamino, (lower-alkyl)-(phenyl)amino, pheg nyl-lower-alkylamino or(lower-alkyl)-(phenyl-lowert I I alkyl)amino; and An is an anion.

\ Particularly preferred embodiments of the abovede- 6 scribedcomposition of matter as ct are as follows:

c An p6 a. Compounds of Formula I wherein A is /C-C=NH HN='CC\ R 1 ijll\Y! I Y/ and Y is Formulal wherein A is a divalent radical combiningwith the E -C=C- portion of the molecule to which it is attached to forma six-membered carbocyclic ring and is selected from the class havingthe formulas of the formula Formula ll R R R R R R R R in which Me, R, RR R Z and An each have the l l l 2 same respective meanings indicated inrelation for For- -c=c c=cand CH-CH-CHCH- 5 mula 4 UMNSM) (7) (6) (5) 1b. Compounds of Formula I wherein A IS wherein each instance C(7) andC(4) are bonded to R R2 Ru C 70 and C 30 respectively, and in which R,R,, R M and R are the same or different and are selected from 60 theclass consisting of hydrogen, alkyl having 1 to 3 carbon atoms, alkoxyhaving I to 3 carbon atoms, halo, triand Y i fluoromethyl, phenyl andphenyl substituted by aikyl having one to three carbon atoms, alkoxyhaving I to 3 carbon atoms and halogen; Me is a metal selected from theclass consisting of copper, cobalt and nickel; Y is a divalent radicalcombining with the S-CC- portion of the molecule to form a five-memberedheteroof the formula Formula ill in which Me, R, R R2, R N=B and An eachhave the same respective meanings indicated in relation to Formula I.

c Compounds of Formula I wherein A is Formula [V in which Me, R, R R Rand 2 each have the same respective meanings indicated in relation toFormula I.

d. Compounds of Formula I wherein A is Formula V in which Me, R, R R Rand N=B each have the same respective meanings indicated in relation toFormula I.

The compounds of Formula I (and Formulas ll, III, IV and V) which aremetal chelates of l-imino-3-(4- imino-S-thiazolidinylidenc)isoindolinesand l-imino-3- (4-imino-Z-thiazolin-S-ylidene)isoindolines, arewaterinsoluble pigments, red in shade, and have improved lightstability. They are useful for coloring natural fibers, syntheticfiber-forming material and cellulosic materials such as threads, sheets,fibers, filaments, textile fabrics and the like, as well as in themanufacture of paper, varnishes, inks, cc rings and plastics. Because oftheir excellent light-fastness, the pigments of this invention areparticularly suitable for the preparation of coatings that are designedfor outdoor exposure such as automotive finishes.

The invention sought to be patented, in a second composition of matteraspect, resides in the novel 1- imino-3-( 4-imino-5 -thiazolidinylidene)isoindolines and l -imino-3-( 4-imino-2-thiazolin-S-ylidene)isoindolines represented by the formula Formula Vl wherein A is adivalent radical combining with the C=C- portion of the molecule towhich it is attached to form a six-membered carbocyclic ring and isselected from the class having the formulas where in each instance C(7)and C(4) are bonded to C( 7a) and C(3a) respectively, and in which R, RR and R are the same or different and are selected from the classconsisting of hydrogen, alkyl having 1 to 3 carbon atoms, alkoxy having1 to 3 carbon atoms, halo, trifluoromethyl, phenyl and phenylsubstituted by alkyl having 1 to 3 carbon atoms, alkoxy having I to 3carboQatoms and halogen; and Y is a divalent radical combining with theSC-C portion of the molecule to form a five-membered heterocyclic ringhaving the same orientation as a thiazole ring and selected from thegroup consisting of and in which Z is NH, O or S, and N=B islower-alkylamino, di-lower-alkylamino, piperidino, pyrrolidino, morpholino, phenylamino, (lower-alkyl)-(phenyl)amino, phenyl-lower-alkylaminoor (lower-alkyl)-(phenyl-loweralkyl)amino.

Particularly preferred embodiments in accordance with its secondcomposition of matter aspect are as follows:

of the formula Formula VII in which R, R R R and Z each have the samerespective meanings indicated in relation to Formula V].

2. The novel 1-imino-3-(4-imino-2-thiazolin-5- ylideneisoindolines ofFormula V] wherein A is and Y is of the formula Formula VIII in which R,R,, R R and N=B each have the same respective meanings given in FormulaVI.

3. The novel l-imino-3-( 4-imino-5- thiazolidinylidene)isoindolines ofFormula VI wherein A is II! T- a --CHCH- H-CH- and Y is CNH- of thefonnula R H NH I c R, I

I NH H c R,

/\R l NH H 1 S/ -i= \ENH Formula IX in which R, R,, R R and Z each havethe same respective meanings given in Formula VI.

4. The novel l-imino-3-( 4-imino-2-thiazolin-5- ylidene)isoindolines ofFormula VI wherein A is and Y is Formula X in which R, R R R and N=Beach have the same respective meanings given in Formula VI.

It will, of course, be understood by those skilled in the art that thecompounds of this invention, both final products and intermediates, mayexist and may be represented in any one of several tautomeric forms.However, structural determinations lead to the conclusion that the formsdepicted by the structural formulas and as named are the most likelyunder ordinary conditions.

In the first of its process aspects, the invention sought to be patentedresides in the process which comprises interacting approximately twomolecular equivalents of a compound of the formula Formula VI orpreferably the zinc halide adduct thereof with approximately onemolecular equivalent of a metal salt, MeAn wherein A, Me, Y and An eachhave the same respective meanings given in relation to Formula I andFormula VI above.

In a second process aspect, the invention sought to be patented residesin the process for preparing the novel I -imino-34-imino-S-thiazolidinylidene )isoindolines and l -imino-3-( 4-imino-2-thiazolin- 5 -ylidene )isoindolines of Formula VI which comprisesinteracting in approximately equimolecular proportions a compound of theformula Formula XI and a compound of the formula Formula XII wherein Aand Y Y have the same respective meanings given in relation to FormulaVI above.

As used throughout, the term halogen" includes bromine, chlorine,fluorine and iodine.

As used herein the term alkyl having I to 3 carbon atoms includessaturated straightor branched-chain aliphatic radicals represented by,for example, methyl, ethyl, propyl and isopropyl.

Similarly, the term alkoxy having l to 3 carbon atoms" includesstraightor branched-chain aliphatic groups attached to the oxygen atomIncluded in this term are, for example, methoxy, ethoxy, propoxy andisopropoxy.

In the above general formula, the radical N=B includes:lower-alkylamino; di-lower-alkylamino; saturated N-heterocyclic groups,such as piperidino, pyrrolidino, morpholino, and lower-alkylatedderivatives thereof (for example, 2-methylpiperidino,3-ethylpyrrolidino, 3-methylmorpholino and the like); phenylamino;(lower-alkyl)-(phenyl)amino; phenyl-loweralkylamino or(lower-alkyl)-(phenyllower-alkyl- )amino. The term lower-alkyl includesalkyl radicals containing from 1 to 6 carbon atoms which can be straightor branched. Included in the lower-alkylamino groups are, for example,methylamino, ethylamino, propylamino, isopropylamino, butylamino, tert.-butylamino, pentylamino and n-hexylamino. In the dilower-alkylaminoradicals the lower-alkyl groups can be the same or different and thusN=B, when it represents a di-lower-alkylamino radical, includes suchgroups as dimethylamino, diethylamino, ethylmethylamino, dipropylamino,dibutylamino, dipentylamino and dihexylamino.

When N=B represents a phenyl-lower-alkylamino group there are includedsuch groups as benzylamino, phenylethylamino, phenylpentylamino; and thelike. When N=B represents a (lower-alkyl)-(phenyl)amino group there areincluded such groups as (methyl)- (phenyl)amino, N(CI I )(C H(ethyl)-(phenyl- )amino, N(C H )(C,,-I-I (isopropyl)-(phenyl)amino,N(i-C H )(C H (butyl)-( phenyl)amino, N(C,H,,)(C H(hexyl)-(phenyl)amino, N(C H, )(C H and the like. In the preferred typesof (lower-alkyl)-(phenyl)amino groups, the lower-alkyl groups have fromI to 6 carbon atoms. When representing(lower-alkyl)-(phenyl-lower-alkyl)amino, N=B includes(methyl)-(benzyl)amino, N(CH (C H CH (ethyl)-(phenylethyl)amino, N(C H)(C H CH CH (propyl)-(benzyl)amino, N(C H )(C I-I -,CH (butyl)-(phenylethyl)amino, N(C H,,)(C,,H CH CH2); and the like. In thepreferred types of (lower-alkyl)-(phenyllower-alkyl)amino groups, thelower-alkyl groups have from I to 6 carbon atoms and the alkyleneradicals of the phenyl-lower-alkyl groups have from l to 4 carbon atoms.

The term anion, as used herein, means a monovalent inorganic or organicanion. The choice of an anion is not critical in the operation of thepreparation processes nor is the identity of the anion a criticalfeature of the claimed products. Accordingly, by way of illustration andwithout limitation thereto, the anion can be, for example, bromide,chloride, iodide, hydroxide, nitrate, acetate, p-toluenesulfonate andthe like. Particularly preferred anions are bromide and chloride becauseof the lower cost and greater availability of the nickel, copper orcobalt salts bearing those anions.

The metal chelate pigments of this invention are useful for coloring orprinting paper and cardboard as well as for coloring paper pulps. Theyare also useful for coloring and printing textile materials made fromnatural fibers, such as wool, cotton or liner, those made fromsemi-synthetic fibers, such as regenerated cellulose as represented byrayon or viscose or those made from synthetic fibers, such aspolyaddition, polycondensation or polymerization compounds. Suchcolorings or printings can be carried out with the subject pigments inaccordance with the usual pigment coloring and printing processes.

The metal chelate pigments of this invention are also useful forincorporation into lacquers and films of various constitution, forexample, those made from celluiose acetate, cellulose propionate,polyvinyl chloride, polyethylene, polypropylene, polyamides, polyestersor alkyd resins. In addition the subject compounds are suitable forcoloring natural or synthetic resins, for example acrylic resins, epoxyresins, polyester resins, vinyl resins, polystyrene resins or alkydresins. When dispersed in a clear coating composition vehicle with theincorporation of a small amount of flake aluminum and the compositionscoated and cured on steel test panels, the subject pigments showexcellent transparency, cleanliness and good intensity.

The metal chelate pigments of this invention are characterized byexcellent light-fastness both under accelerated exposure evaluations andunder prolonged outdoor exposure. Thus, when the subject pigmentssuspended in cured acrylic resin dispersion coated on foil-covered paperare exposed to carbon arc radiation, there is no loss in color value ofthe pigments after 300 hours of continuous exposure. Moreover, whensteel plates coated with a cured acrylic resin dispersion of the subjectpigments were exposed for 12 months in Florida, there was substantiallyno loss in color value or any indication of darkening.

The best mode contemplated by the inventors of carrying out thisinvention will now be described as to enable any person skilled in theart to which it pertains to make and use the same.

Generally speaking, the novel metal chelate pigments of Formula I areconveniently obtained by interacting approximately two molecularequivalents of the appropriatel-imino-3-(4-imino-S-thiazolidinylidene)isoindoline or l-imino- 3-(4-imino-2-thiazolin-5 ylidene)isoindoline of Formula VI with onemolecular equivalent of a metal salt, MeAn wherein Me and An have thesame meanings given hereinbelow. The reaction is preferably carried outat a temperature between about 0C and lO0C in either an aprotic orprotic solvent. Aprotic solvents suitable for the reaction are, forexample, dimethylformamide, dimethylsulfoxide andhexamethylphosphoramide. Among protic solvents useful for this reactionare, for example, water; loweraliphatic alcohols, for instance,methanol, ethyl alcohol, isopropyl alcohol, etc.; and ether glycols, forinstance, Z-methoxyethanol, Z-ethoxyethanol, etc.

An alternate and preferred procedure for preparing the metal chelates ofFormula I is carried out by inter acting approximately two molecularequivalents of a zinc halide adduct of the appropriate l-imino-3-(4-imino-S-thiazolidinylidene)isoindoline or l-imino-3- 1 1(4-imino-Z-thiazolin-S-ylidene)isoindoline of Formula V] with onemolecular equivalent of a metal salt, MeAn wherein Me and An have thesame meanings given hercinabove. The reaction using the zinc halideadduct is preferably carried out at a temperature between about C and100C in an aprotic solvent, for example, dimethylformamide,dimethylsulfoxide, hexamethylphosphoramide, etc. The requisite zinchalide adduct is readily obtained by treatment of the appropriatel-imino-3-(4imino-5-thizolidinylidene)isoindoline orl'imino-3-(4-imino-2-thizolin-2-ylidene)isoindoline with a solution ofthe zinc halide in an aprotic solvent, for example, dimethylformamide.Although the adduct, which is initially obtained as a solid suspended inthe aprotic solvent may be subjected without isolation to interactionwith the chelating metal salt, we generally prefer to separate theproduct by filtration prior to its use for forming the metal chelatepigment. Particularly preferred zinc halides for preparation of theadduct are zinc chloride and zinc bromide and particularly preferredtemperature for the preparation of the metal chelates, either directlyor by way of the zinc halide adduct, is at a temperature between aboutand 50C.

We have also found that the novel metal chelate pigments of Formula Iare obtained by first interacting approximately two molecularequivalents of the appropriate l,3-diiminoisoindoline with one molecularequivalent of a metal salt, MeAn followed by the addition ofapproximately two molecular equivalents of the appropriateiminothiazolidine or iminothiazoline. The same general conditions ofreaction, that is, temperature and solvent system described for thepreparative methods described above are also applicable to thissynthetic approach.

The metal chelate pigments of this invention which bear either of thepreferred anions, bromide or chloride, are, of course, obtained bydirect chelation of the appropriate compound of Formulas VII, VIII, lXor X with the appropriate metal (ll) bromide or chloride. However, wehave found that corresponding metal chelate pigments bearing hydroxideas the anion are obtained by employing a metal (ll) salt in which theanion is organic in nature. For example, when the appropriate l-imino-3(4-imino-5-thiazolidinylindene )isoindoline or l-imino-3-(4-imino-2-thiazolin-5-ylidene)isoindoline is subjected to interactionwith the appropriate bydrated metal (ll) p-toluenesulfonate in thepresence of dimethylformamide, the anion obtained is hydroxide. The sameresult is also obtained by anion exchange. Thus, when the correspondingmetal chelate pigment bearing a halide as the anion is heated forseveral hours in the presence of aqueous methanesulfonic acid, thehalide is replaced by hydroxide. On the other hand, for reasons that arenot completely understood, we have found that heating the same metalchelate pigment bearing halide as the anion with aqueousp-toluensulfonic acid for several hours, yields the corresponding metalchelate pigment bearinig a p-toluenesulfonate anion.

The novel l-imino-3-(4-imino-5- thiazolidinylidene)isoindolines andl-imino-3-(4- imino-2-thiazolin-5-ylidene)isoindolines represented byFormula VI, which are used to prepare the metal chelate pigments ofFormula I are readily prepared by the condensation of the appropriatel,3-diiminoisoindoline through one of the imino moieties with the lossof ammonia at the site of the active methylene moiety of the appropriate4-iminothiazolidine or 4-imino-2- thiazoline. The iminothiazolidines andiminothiazolines used in the preparation are generally unstable in thefree-base form and are preferably employed in the form of their acidaddition salts, for example, the hydrochlo' ride, benzenesulfonate, etc.The reaction proceeds smoothly at reflux in a lower-aliphatic alcoholsuch as methanol and is preferably carried out under an atmosphere ofnitrogen. When the acid addition salt is used in the reaction, theresultant l-imino-3-(4-imino-5- thiazolidinylindene)isoindoline orl-imino-3-(4-imino- Z-thiazolin-S-ylidene)isoindoline separates in theform of an acid addition salt which is converted to its freebase form bytreatment with a slight excess of a base, such as triethylamine.Alternatively, the acid addition salt form of the iminothiazolidine oriminothiazoline can be converted initially to the free-base form in situby the addition of a stoichiometric quantity of a base to the reactionmixture prior to the addition of the 1,3- diiminoisoindoline.

The l,3diiminoisoindolines of Fromula XI required for the preparation ofthe novel l-imino-3-(4-imino-5- thiazolidinylidene)isoindolines and thel-imino-3-(4- imino-2-thiazolin-S-ylidene)isoindolines of Formula Vl area known class of compounds readily obtained by procedures well-known inthe prior art. lcf. e.g. (l) Angnew. Chem. 68, 133 (1956); (2) J. Chem.Soc. 3525 (1955); (3) British Pat. Specification 698,049]. For example,an appropriate phthalonitrile is interacted with ammonia or with asubstance which gives off ammonia under the reaction conditions, forinstance, urea to obtain the corresponding 1,3- diiminoisoindoline. Forexample, the following 1,3- diiminoisoindolines of Formula XI are usefulstarting materials for preparing both the l-imino-3-(4-imino-5-thiazolidinylidene)isoindolines and the l-imino-3-(4-imino-Z-thiazolin-S-ylidene)isoindolines represented by Formula Vlabove. Those intermediates in the following list whose physicalproperties and/or preparation are described in the above-mentionedreferences, (1), (2) or (3), are so indicated.

l,3-Diiminoisoindoline, mp l-l82C (dec) (1) 4,5 ,6,7-Tetrahydrol,3-diiminoisoindoline,

l77-l80C (dec) (2) S-Methyl-1,3-diiminoisoindoline, mp l89l90C (dec)4,5-Dimethyll ,3-diiminoisoindoline 5,6-Dimethyl-4,5,6,7-tetrahydro-l,3-diiminoisoindoline 4,5 ,6,7-Tetraethyll ,3-diiminoisoindoline 4,5,7-Trimethyll ,3diim inoisoindoline 4-lsopropyl-7-methyl-l,3-diiminoisoindoline 4,7-Dimethoxyl ,B-diiminoisoindoline 5,6-Dimethoxy-4,5 ,6,7-tetrahydrol ,3-diiminoisoindoline4,5-Dipropyl-7ethoxy-l ,3-diiminoisoindolineS-ethoxy-l,3-diiminoisoindoline, mp 2l7-2l8C (3) 4,5 ,7-Trimethoxyl,3-diiminoisoindoline 4,7-Diethoxyl ,3diiminoisoindoline 4-chlorol,3-diiminoisoindoline (3) S-Bromol ,3-diiminoisoindoline 5-Chloro-4,5,6,7-tetrahydro-l ,3-diiminoisoindoline5,6-Dichloro-l,3-diiminoisoindoline, mp 265C (dec) 4,5,6,7 -Tetrachlorol,B-diiminoisoindoline,

295300C (dec) (l 5 ,6-Dibromo-4,7-difluorol ,3-diiminoisoindoline5-Chloro 4,6,7-trifluorol ,3-diiminoisoindoline4-Bromo-6-methyl-4,5,6,7-tetrahydrol ,3-

diiminoisoindoline 5,6-Diiodo-4,7-dimethoxyl ,3-diiminoisoindoline4,7-Difluoro-l ,B-diiminoisoindoline 4,5 ,6,7-Tetrabromo- 1,3-diiminoisoindol ine S-Phenyll ,3-diiminoisoindoline4-Methyl-5,6,7-triphenyll ,3-diiminoisoindoline5-Methyl-4-phenyl-4,5,6,7-tetrahydrol ,3-

diiminoisoindoline 4-(3,4-Dimethoxyphenyl)-4,5,6,7-tetrahydro-1,3-

diiminoisoindoline 7-Ethoxy-4-methyl-5-ohr:nyl-l ,3-diiminoisoindoline4-( p-Chlorophenyl )4,5,6,7-tetrahydro-l ,3-

diiminoisoindoline I -(p-Bromophenyl)-7-phenyl- 4,5 ,6,7-tetrahydro-l,3-diiminoisoindoline 4,5 ,7-Triphenyl-4,5 ,6,7-tetrahydrol,3-diiminoisoindoline 4,5 ,7-Triphenyl-4,5,6,7-tetrahydro-1,3-diiminoisoindoline 4,5,6,7-Tetraphenyl-l,3-diiminoisoindoline 5-(2,4,5-Trimethylphenyl)-1,3-diiminoisoindolineAn alternate but similar route to the preparation of the novell-imino-3-( 4-imino-5- thiazolidinylidene)isoindolines and limino-3-(4-imino-2-thiazolin-5-ylidene)isoindolines represented by Formula Vlcomprises the condensation of the appropriatel-imino-3-lower-alkoxyisoindoline or imino-3-mercaptoisoindoline throughthe alkoxy or mercapto moiety respectively at the site of the activemethylene moiety of the appropriate 4-iminothiazolidine or4-imino-2-thiazoline. Although either the appropriate1-imino-3-lower-alkoxyisoindoline or 1- imino-3-mercaptoisoindoline maybe substituted in the preparative route described above which utilizesthe appropriate 1,3-diiminoisoindoline, a particularly convenientprocedure involves in a single operation the in situ formation of thel-imino-3-lower-alkoxyisoindoline or l-imino-B-mercaptoisoindoline andthe condensation thereof with the appropriate iminothiazolidine oriminothiazoline. Thus, in a manner taught in the prior art anappropriate phthalonitrile is treated at ambient temperature in alower-aliphatic alcohol, such as methanol, with one molecular equivalentof either a sodium lower-alkoxide to obtain thel-imino-3-loweralkoxyisoindoline or with sodium sulfide to obtain thecorresponding sodio derivative of l-imino-3-mercaptoisoindoline. Thenunder an atmosphere of nitrogen one molecular equivalent of theappropriate iminothiazolidine or iminothiazoline in the form of the acidaddition salt is added to the stirred reaction mixture at 0C andstirring is continued for approximately 16 to l8 hours whilst permittingthe reaction to warm gradually to room temperature.

The thiazolidines represented by Formula XII when Y is and theZ-thiazolines when Y is which are required for condensation with the L3-diiminoisoindolines to obtain the novel l-imino-3-(4-imino-5-thiazolidinylidene)isoindolines and the l imino-3-(4-imino-2-thiazolin- 5 ylidene) isoindolines, respectively, of FormulaVl are generally known in the art and are conveniently prepared byemploying known chemical procedures. For example, the known 2,4-diiminothiazolidine (Formula Xll where Y is is obtained by theinteraction of a haloacetonitrile with thiourea.

The starting material, 2,4diiminothiazolidine, also serves as thestarting material for the preparation of the known compound,4-imino-2-thiazolidinone (Formula XII where Y is Thus,2,4-diiminothiazolidine is in a first step hydrolyzed to obtain2,4-dioxothiazolidine which is then in the second step interacted withphosphorus pentasulfide to obtain 2-oxo-4-thioxothiazolidine. Finally,in a third step, this intermediate is treated with ammonium hydroxide toconvert the 4-d1ioxo moiety to an imino group thus yielding the desired4-imino-2-thiazolidinone.

The starting material 4-imino-2-thiazolidinethione (Formula XII where Yis is similarly prepared by first interacting commercially available4-oxo-2-thioxothia2olidine with phosphorus pentasulfide to produce2,4-dithioxothiazolidine which upon treatment with ammonium hydroxideyields the desired 4-imino- Z-thiazolidinethione.

The 2-amino-substituted-4-imino-2-thiazoline starting materials depictedby Formula Xll wherein Y represents are conveniently prepared by theinteraction of a haloacetonitrile and the appropriately substitutedthiourea of the formula wherein N=B has the same respective meaningsgiven for Formulas l, Ill, V, VI and VIII above. For example, thefollowing compounds of Formula Xll (named as the free base) are usefulstarting materials for condensation with the l,3-diiminoisoindolinestarting materials described above for obtaining the novel l-imino-3-(2- arnino-substituted-4-imino-2-thiazolin-5-ylidene )isoindolines ofFormula VI in which Y is N=B.

Z-Methylamino-4-imino-2-thiazoline 2-lsopropylamino-4-imino-2-thiazoline2-( Z-Methylbutylamino )-4-imino-2-thiazoline2-n-Hexylamino-4-imino-2-thiazoline 2-Anilino-4 imino-2-thiazoline2-Diethylamino-4-imino-2 -thiazoline2-N-Methylethylamino-4-imino-2-thiazoline2-Di-t-butylamino-4-imino-2thiazoline2-Di-n-hexylamino-4-imino-2-thiazoline2-Benzylamino-4-imino-2-thiazoline 2-( S-Phenylpropylamino)-4-irnino-2-thiazoline 2-( S-Phenylpentylamino )-4-imino-2-thiazolineZ-N-Ethylan ilino-4-imino-2-thiazoline 2-N-Butylanilino-4-imino-2-thiazoline Z-(p-Ethylanilino )-4-imino-2-thiazoline2-Dibenzylamino-4-imino- 2-thiazoline2-n-Ethylbenzylamino-4-imino-2-thiazoline 2-( p-Chloroanilino )-4-imino-2-thiazoline 2-(o-Methoxyanilino l-4-imino-2-thiazole Z-N- Methyl(p-bromobenzy lamino )-4-imino-2-thiazole2-Pyrrolidino-4-imino-2-thiazoline 2-Piperidino-4-imino-2-thi azoline2-Morpholino-4-imino-2-thiazoline 2-( 2-Methylpiperidino)-4-imino-2-thiazoline 2( 3-Ethylpyrrolidino)-4-imino-2-thiazoline 2-(3-Methylmorpholino -4-imino- 2-thiazoline The structures of thecompounds of this invention were established by the modes of synthesis,by elementary analyses of representative samples, and by ultraviolet,infrared and nuclear magnetic resonance spectral analyses. The course ofthe reactions for the preparation of the intermediates and theirconsumption in the chelating reactions was followed by the use of thinlayer chromatography.

The invention is illustrated by the following examples without, however,being limited thereto. Melting points are uncorrected unless otherwiseindicated.

EXAMPLE 1 A. To a stirred solution of 61 parts of the 28 percent aqueousammonium hydroxide solution and 2500 parts of water under an atmosphereof nitrogen there was simultaneously added at ambient temperature duringa period of ninety minutes 273 parts of 2,4-diiminothiazolidiniumbenzenesulfonate and 853 parts of a 17.1 percent by weight methylalcohol solution of 1,3- diiminoisoindoline. A yellow solid separatedduring the addition. Stirring was continued at room temperature forapproximately 16 hours after the additions were complete and the thickyellow reaction slurry was then filtered. The product collected on thefunnel was washed copiously with distilled water and finally dried at50C in vacuo to obtain 233 parts of l-imino3-(2,4-diimino-S-thiazolidinylidene)-isoindoline as a yellow solid melting at252263C. (dec).

Anal. Calcd. for C H N S: C,54.30; H,3.73;

N,28.79; 5,1 3.18. Found: C,54.15; H, H385, N,28.63; 5,1292. Thiscompound, which corresponds to Formula VII wherein R, R R and R are eachhydrogen, and Z is NH, was found on testing in vitro by standard serialdilution procedures to be bacteriostatic versus Salmonella rypliosaHopkins at a concentration of 250 parts per million and bactericidal at750 parts per million; and both bacteriostatic and bactericidal versusClo stridium welc'hii M at 100 parts per million.

B. To a stirred solution of 150 parts of zinc chloride in 2280 parts ofdimethylformamide there was added at ambient temperature 243 parts ofl-imino-3-(2,4- diimino-Sthiazolidinylidene)-isoindoline which went intosolution. After approximately 5 to 10 minutes of continued stirring, thezinc chloride adduct began to separate from the reaction mixture as ayellow precipitate. Stirring at room temperature was continued overnightafter which the product was collected by filtration, washed first withfresh dimethylformamide, then with acetone and finally dried in a vacuumoven at 50C to obtain 390 parts of the zinc chloride adduct ofl-imino-3-( 2,4-diimino-5-thiazolidinylidene )isoindoline as a yellowpowder which melted at 337338C (dec).

Anal. Calcd. for C H N S ZnCl C,35.28; H,2.44; N,18.50; S,8.46;Cl,l7.94; Zn,16.68. Found: C,34.8l; l1,2.39; N,l3.45; 5.8.45; Cl,l8.68;Zn,17.22.

When the above-described procedure was employed but zinc bromide wasused in place of zinc chloride, the zinc bromide adduct of1-imino-3-(2,4-diimino-5- thiazolidinylidene)isoindoline was obtained asa yellow powder which melted at 347348C (dec).

C. To a stirred solution of 130.5 parts of nickel (ll) chloridehexahydrate in 2260 parts of dimethylformamide, there was added at roomtemperature 380 parts of the zinc chloride adduct ofl-imino-3-(2,4-diimino- S-thiazolidinylidene)isoindoline from B. Thereaction slurry was then stirred at ambient temperature for a period of4 hours during which the mixture gradually changed from yellow to deepred. During the next 2 hours, the slurry was gradually heated to C andwas maintained at that temperature for 4 hours. Ammonia was evolvedduring the reaction period. The suspended red solid was then collectedby filtration, washed successively with fresh dimethylformamide, waterand finally acetone. The solid was then dried in vacuo at 50C to obtain285 parts of the blue-red nickel chelate pigment represented by Formula11 wherein Me is Ni; Z is NH; R, R R and R are each hydrogen and An isCl.

Anal. Calcd. for C H ClN NiS C,46.96; H,2.50; (16.31; N,22.41; Ni,10.43;S,l1.40. Found: Q4397; H281; Cl,5.66; N,20.2l; Ni,9.76; 8,1065; HO,7.4S. (On dry basis) C,47.5 l; H,2.23; Cl,6.l l; N.2l.84; Ni,10.55;8.11.51.

EXAMPLE 2 A mixture of 4.35 parts of 1,3-diiminoisoindoline and 50 partsof dimethylformamide was stirred and heated to 50C to effect completesolution. The solution was cooled to a temperature in the range 15 to20C and there was then added a solution of 3.92 parts of nickel (ll)chloride hexahydrate in 30 parts of dimethylformamide. Stirring wascontinued for 30 minutes after the addition during which period a yellowsolid gradually deposited from the solution. To the stirred suspensionthere was then added 8.2 parts of 2,4-diiminothiazolidiniumbenzenesulfonate. Stirring was continued at room temperature forapproximately 16 hours. A red solid gradually separated from thereaction mixture during the stirring period. The mixture was then heatedat 100C for 5 hours after which the product was collected by filtration,washed successively with dimethylformamide, water and acetone. Theproduct was dried in vacuo to obtain 7.3 parts of the nickel chelatepigment which corrcsponds to Formula ll wherein Me is Ni; Z is NH; R, RR and R are each hydrogen;

17 and An is C1. The product has the same blue-red shade as the productobtained in Example 1, part C, above.

EXAMPLE 3 A. A mixture of 25.5 parts ofl,3-diimino-4,5,6,7-tetrachloroisoindoline, 13.65 parts of2,4-diiminothiazolidine hydrochloride and 600 parts of dimethylformamidewas stirred and heated under an atmosphere of nitrogen at a temperaturein the range 65 70C for approximately 16 hours. The reaction mixture wasthen cooled to C and filtered. The collected solid was washed with 60parts of fresh dimethylformamide, slurried with 1200 parts of a 10percent aqueous solution of sodium carbonate and then refiltered. Thecollected solid was recrystallized from hot glacial acetic acid toobtain l-imino-4,5 ,6,7-tetrachloro-3-( 2,4-diimino-5-thiazolidinylidene)isoindoline acetate as a brown powder melting withgradual decomposition above 200C.

Anal. Calcd. for C Cl H N S C H O C,35.39; H,2.06; C132. N,15.88;5,7.27. Found: C,35.47; H,2.15; C1,32.87; N,16.1 l; 8,743.

This compound, which corresponds to Formula V11 wherein R, R,, R and Rare each Cl, and Z is NH, was found on testing in vitro by standardserial dilution procedures to be bacteriostatic versus: Staphylococcusaureus 209 at a minimal concentration of 31.3 parts per million;Pseudomonas aeruginosa 21 1 at 62.5 parts per million; Esherichia coliat 62.5 parts per million; and Proteus vulgaris ATCC 9920 at 125 partsper million.

B. To a stirred solution of 2.5 parts of nickel (ll) chloridehexahydrate in 500 parts of hexamethylphosphoramide, there was added atroom temperature during a period of 30 minutes, 7.6 parts ofl-imino-4,5,6,7- tetrachloro-3 2,4-diimino-S-thiazolidinylidene)-isoindoline obtained by treating the acetate-salt form of A above withmethanolic triethylamine. After the addition was complete, the reactionmixture was stirred at room temperature for 16 hours and then filtered.The collected solid was washed with fresh hexamethylphosphoramide, thenwith water and finally dried in vacuo at 100C to obtain the dark-redpigment corresponding to Formula 11 in which Me is Ni; Z is NH; R, R,, Rand R are each C1; and An is Cl.

Anal. Calcd. for C H Cl N NiS C,3l.52; H,0.27; Cl,38.06; N,15.04;Ni7.01; 5,7.65. Found: C,31.36; H,0.73; Cl,37.88; N,l4.97; Ni,7.29;S,7.74.

EXAMPLE 4 A. A mixture of 3.5 parts of 4-imino-2-thiazolidinone, 4.4parts of 1,3-diiminoisoindoline and 100 parts of methanol was stirredunder an atmosphere of nitrogen at room temperature for 3 hours and thenat reflux temperature for 2 hours. The reaction mixture was cooled to25C and the solid therein was collected by filtration, washed with freshmethanol and dried in vacuo at 50C. to obtain 5 .4 parts of l-imino-3-(2-oxo- 4-imino-5(-thiazolidinylidene)isoindoline) as a yellow powdermelting at 346348C. (dec).

Anal. Calcd. for C l-l,,N,OS (M.W. 244.25): N,22.94; S,13.13.

Found: N,23.00; 8,1328.

Mass spectrum determination showed a parent peak at M 244. This compoundcorresponds to Formula Vll wherein R, R R and R are each hydrogen and Zis O.

B. To a stirred solution of 2.7 parts of nickel toluenesulfonatehexahydrate in 100 parts of dimethylformamide there was added at roomtemperature 2.44 parts of l-imino-3-( 2-oxo-4-imino-5-thiazolidinylidene )isoindoline. The temperature of thereaction mixture was gradually raised to reflux over a period of 3 hoursand maintained for an additional hour. The reaction mixture whichgradually changed color from yellow to dark red during the heatingperiod, was cooled to 25C and the solid therein collected by filtration.After successive washings with dimethylformamide, water and tinallyacetone, the solid was dried in vacuo to obtain 2.2 parts of the redpigment represented by Formula 11 in which Me is Ni, Z is O; R, R,, Rand R are each hydrogen; and An is OH.

Anal. Calcd. for C H, N,NiO S C,48.46, H,2.22; N,l7.98; Ni,l0.77; S,11.77. Found: C,48.96; H,2.l6; N,l8.0l; Ni,10.90;S,11.64.

EXAMPLE 5 Three parts of the nickel (ll) chloride chelate pigmentobtained in Example 1C above was dissolved in 39 parts ofmethanesulfonic acid at approximately C under an atmosphere of nitrogen.To the stirred solution was added 19.2 parts of water after whichheating was effected to and held at 125C for 5 hours. A red solidgradually separated during the heating period. The reaction mixture wascooled to 25C and liltered. The collected solid was washed successivelywith aqueous methanesulfonic acid, water and acetone and finally driedin vacuo to obtain the nickel chelate pigment represented by Formula 11wherein Me is Ni; Z is O; R, R R and R are each hydrogen; and An is OH.This product was of the same shade and hue as that obtained in Example4, part B, above and had an infrared spectrum identical to that obtainedfor the product of Example 4, part B above.

Anal. Calcd. for C H N NiO S C,48.46; H,2.22; N,l7.98; Ni,l0.77;S,l1.77. Found: C,48.30; H,2.33; N,l7.74; Ni,l0.55; S,11.l4.

EXAMPLE 6 To a stirred solution of 178 parts of p-toluenesulfonic acidin 22 parts of water warmed to approximately C, there was added tenparts of the nickel (ll) chloride chelate pigment obtained in Example 1Cabove. The reaction mixture was heated at reflux for a period ofapproximately 19 hours during which a red solid gradually separated. Thesolid was collected by filtration and washed successively with a 70percent aqueous solution of p-toluenesulfonic acid, water, and tinallyacetone. The product was dried in vacuo to obtain 8.8 parts of theblue-red pigment corresponding to Formula 11 wherein Me is Ni; R, R Rand R are each hydrogen; Z is O; and An is p-(CH )C H SO Anal. Calcd.for C ,,H,,,N,NiO S C,49.73; H,2.73; N,l4.00; Ni,8.38', S,l3.73. Found:C,49.59; H,2.82; N,l4.19; Ni,8.15; S,l3.60.

EXAMPLE 7 To a stirred suspension of 9.7 parts of l-imino-3-(2,4-diimino-5-thiazolidinylidene)isoindoline in parts ofhexamethylphosphoramide there was added 3.45 parts of copper (ll)chloride dihydrate. The reaction mixture was stirred at room temperaturefor approximately 16 hours and was then heated to and held at 100C for 4hours. The mixture was filtered and the collected solid was washed withfresh hexamethylphosphoramide and finally with water. The product wasdried in vacuo to obtain the dark red copper chelate pigment representedby Formula 11 wherein Me is Cu; Z is NH; R, R R and R are each hydrogen;and An is EXAMPLE 8 Following the procedure described above in Example7, but substituting 4.8 parts of cobalt (ll) chloride hexahydrate forthe copper (ll) chloride dihydrate used in that example, there wasobtained the brown cobalt chelate pigment corresponding to Formula 11wherein Me is Co; Z is NH; R, R R and R are each hydrogen; and An is Cl.

EXAMPLE 9 A. A mixture of 33.1 parts of l-piperidyl thiocarbamide, 140parts of ethyl alcohol and 17.4 parts of chloroacetonitrile was heatedat reflux for one and one-half hours. The reaction mixture was thenchilled in an ice bath to less than 10C and filtered. The whitecrystalline solid isolated by the filtration was dried to obtain 26parts of 2 piperidino-4-imino-Z-thiazoline hydrochloride which graduallysoftened above 200C and decomposed at 321C. An additional 21 parts ofthe product were obtained by concentrating the filtrate.

Anal. Calcd. for cgH aNas HCl: C,43.73; H,6.42; Cl,l6.l3; N.l9.l2;S,l4.59. Found: C,43.77; H,6.36; Cl,l6.l4; N,l9.25; 8.14.56.

B. To a solution of 21.9 parts of 2-piperidino-4- imino-Z-thiazolinehydrochloride in 240 parts of methyl alcohol there was added 14.5 partsof 1,3- diiminoisoindoline. The resultant mixture was heated at refluxfor six hours, then chilled to C and filtered. The collected solid waswashed with methyl alcohol and dried at 50C to obtain 27 parts ofl-imino-3-(2- piperidino-4imino-2-thiazolin-5-ylidene )isoindolinehydrochloride melting at 320-32lC (dec). The assigned chemical structurewas completely corroborated by a concordant nuclear magnetic resonancespectrum. The hydrochloride salt is readily converted to the free base,a colorless solid melting at 226227C, by treatment with dilute ammoniumhydroxide. This compound corresponds to Formula Vlll wherein R, R R andR are each hydrogen and N=B is piperidino.

C. To a solution of 0.5 part of nickel (ll) chloride hexahydrate in 40parts of methyl alcohol there was added at 25C 1.2 parts ofl-imino-3-(2-piperidino4- imino-2-thiazolin-5-ylidene )isoindoline. Adeep red solution resulted which was stirred at 25C for 2 hours and wasthen heated at reflux for 2 hours. To the solution there was added 80parts of dioxane. The solid, which separated from the solution, wascollected by filtration, washed with 75 percent aqueous dioxane solutionand finally dried in vacuo at 100C to obtain 1.] parts of dark redpigment which remained unmelted at 345C. This product, which correspondsto Formula 111 wherein Me is Ni; R, R,, R and R are each hydrogen; N=Bis piperidino; and An is Cl, was found to be solvated by one mole ofwater and one mole of methyl alcohol.

Anal. Calcd. for C H ClN NlS ChgOH H20: C.52.9l; H,4.84; C1,4.74;N,l6.83; Ni,7.84; 8,8.56. Found: C,52.36; H420; Cl,4.42; N,l6.07;Ni,7.73; 8.8.35.

Nuclear magnetic resonance spectrum was concordant for the solvatedassigned structure.

EXAMPLE 10 A. A mixture of 6 parts of 2,4-diiminothiazolidinehydrochloride, 6 parts of 4,5,6.7-tetrahydro-l,3' diiminoisoindoline and100 parts of anhydrous methyl alcohol was stirred and heated at refluxunder an atmosphere of nitrogen for approximately 16 hours. The reactionwas then cooled and filtered. The solid product collected by filtrationwas converted to the free base by treatment with a slight excess of amethyl alcohol solution of triethylarnine and the product thus obtainedwas recrystallized from acetic acid. The resultant acetate salt wastreated with dilute ammonium hydroxide and the product isolated toobtain in the free-base form 1- imino-4,5 ,6,7-tetrahydro-3-(2,4diimino-5- thiazolidinylidene)isoindoline as a greenish-brown powdermelting at 2l5223C (dec).

Anal. Calcd. for C H N S: (3,5342; H,5.30;

N,28.32; 8,1296. Found; C,53.37; H.529; N,28.20; 5.13.10. This compound,which corresponds to Formula lX wherein R, R R and R are each hydrogenand Z is NH, was found on testing in vitro by standard serial dilutionprocedures to be bacteriostatic versus: Staph ylococcus aureus 209 at aminimal concentration of 31.3 parts per million; Pseudomrmas aeruginosa211 at parts per million; Esherichiu wli at 125 parts per million; andProteus vulgaris ATCC 9920 at 125 parts per million.

B. Following a procedure similar to that described in Example 3, part Bhereinabove, 7.3 parts of the limino-4,5 ,6,7-tetrahydro-3-(2,4-diimino-5- thiazolidinylidene)isoindoline obtained in A, wasinteracted with 3.75 parts of nickel (ll) chloride hexahydrate in 350parts of hexamethylphosphoramide to obtain the dark blue-red pigmentcorresponding to Formula 1V wherein Me is Ni; R, R R and R are eachhydrogen; Z is NH; and An is Cl.

Anal. Calcd. for C 2H22ClN9NiS-z: C,46.31; H,3.89; Cl.6.2l; N,22.08;Ni,l0.29; 5.11.24. Found: C,46.50', H382; C1608; N.22.10; Ni,l0.48; S,l1.30.

EXAMPLE 1 l A. When an equivalent amount of 4-imino-2-thiazolidinethione is substituted for the 4-imino-2- thiazolidinone usedin the procedure described in Example 4, part A above, there is obtainedas the product 1 -imino-3 2-thioxo-4-imino-5- thiazolidinylidene)isoindoline.

B. Following the procedure described in Example 4, part B above butusing an equivalent amount of imino-3-(2-thioxo-4-imino-5-thiazolidiny1idene )isoindoline in place of1-imino-3-( 2-oxo-4-imino-5- thiazolidinylidene)isoindoline, there isobtained as the product a metal chelate pigment corresponding to Formulall in which Me is Ni; Z is S; R, R R and R are each hydrogen; and An isOH.

EXAMPLE 12 A. When equivalent amounts of 2-methylamino-4-imino-2-thiazoline hydrochloride and 5,6-dichloro-l ,3-diiminoisoindoline are substituted for the 2,4-diiminothiazolidinehydrochloride and l,3-diimino-4,5,6,7-tetrachloroisoindolinerespectively in the procedure described in Example 3, part A above,there is obtained as the product1-imino-5,6-dichloro-3-(2-methylamino-4- imino-Z-thiazolin-5ylidene)isoindoline acetate.

B. Following the procedure described in Example 3, part B above butusing an equivalent amount of limino-S ,6-dichloro-3-( 2methylamino-4-imino-2- thiazolin5-ylidene)isoindoline acetate in placeof limino-4.5 ,6,7-tetrachloro-3-( 2 ,4-diimino-5-thiazolidinylidene)isoindoline acetate, there is ob- 21 tained as theproduct a metal chelate pigment corresponding to Formula lll in which Meis Ni; =B is HNCH R and R are each hydrogen; R, and R are each Cl; andAn is Cl.

EXAMPLE l3 A. When an equivalent amount of 4,5-dipropyl-7-ethoxy-l,3-diiminoisoindoline is substituted for the l-3-diiminoisoindoline used in the procedure described in Example 1, partA above, there is obtained as the productl-imino-4,5-dipropyl-7-ethoxy-3-(2,4-diimino-5-thiazolidinylidene)isoindoline.

B. Following the procedure described in Example 7 above but using anequi' ilent amount of l-imino-4,5- dipropyl-7-ethoxy-3-( 2,4-diimino-5-thiazolidinylidene)isoindoline in place of l-imino-3-(2,4-diimino-S-thiazolidinylidene)isoindoline, there is obtained as theproduct a metal chelate pigment corresponding to Formula ll in which Meis Cu; 2 is NH; R is OC H R and R are each C H R, is hydrogen; and An isCl.

EXAMPLE l4 A. When equivalent amounts of 5-methyl-l,3 diiminoisoindolineand 4-imino-2-thiazolidinethione are substituted for the1,3-diiminoisoindoline and 4- imino-2-thiazolidinone respectively, inthe procedure described in Example 4, part A above, there is obtained asthe product l-imino-5-methyl-3-(2-thioxo-4-imino- S-thiazolidinylidene)isoindoline.

B. Following the procedure described in Example 4, part B above butusing an equivalent amount of limino-5-methyl-3 2-thioxo-4-imino-5thiazolidinylidene)isoindoline in place of l-imino-3-( 2-oxo-4-imino-5-thiazolidinylidene)isoindoline, there is obtained as theproduct a metal chelate pigment corresponding to Formula ll in.which Meis Ni; 2 is S; R is CH R, R, and R are each hydrogen; and An is OH.

EXAMPLE 15 A. When equivalent amounts of 4,5,6',7-tetraethyl-1,3-diiminoisoindline and 2-isopropylamino-4-imino- Z-thiazolinehydrochloride are substituted for the 1,3- diiminoisoindoline and2-piperidino-4-imino-2-thiazoline hydrochloride respectively, in theprocedure described in Example 9, part B above, there is obtained as theproduct l-imino-4,5,6,7-tetraethyl-3-(2-isopropylamino-4-imino-2-thiazolin-5-ylidene)isoindolinehydrochloride.

B. Following the procedure described in Example 9, part C above butusing an equivalent amount oflimino-4,5,6,7-tetraethyl-3-(2-isopropylamino-4-imino-2-thiazolin-5-ylidene)isoindoline in the free-base form in place ofl-imino-3-( 2-piperidino-4-imino-Z-thiazolin-S-ylidene)isoindoline,there is obtained as the product a metal chelate pigment correspondingto Formula lll in which Me is Ni; R, R,, R and R are each C 14 N=B isiso-C H,NH; and An is Cl.

EXAMPLE 16 A. When equivalent amounts of 4,7-dimethoxy-l,3-diiminoisoindoline and 2-(2-methylbutylamino)-4- imino-2-thiazolinehydrochloride are substituted for the l,3-diiminoisoindoline and2-piperidino-4-imino-2- thiazoline hydrochloride respectively, in theprocedure described in Example 9, part B above, there is obtained as theproduct l-imino-4,7-dimethoxy-3-[2-(2-methyl- 22butylamino]-4-imino-2-thiazolin-S-ylidene]isoindoline hydrochloride.

B. Following the procedure described in Example 9. part C above butusing an equivalent amount of 1- imino-4,7-dimethoxy- 1-2-(2-methylbutylamino)-4- imino-Z-thiazolin-S-ylidenc ]isoindoline inthe freebase form in place of l-imino-3-(2-piperidino-4-imino-Z-thiazolin-S-yldiene)isoindoline, there is obtained as the product ametal chelate pigment corresponding to Formula lll in which Me is Ni; Rand R are each OCH R, and R are each hydrogen; N= is NHCH CH(CH )CH CHand An is Cl.

EXAMPLE l7 A. When equivalent amounts of 4-chloro-l ,3diiminoisoindoline and 2-n-hexylamino-4-imino-2- thiazolinehydrochloride are substituted for the 1,3- diiminoisoindoline and2-piperidino-4-imino-2-thiazoline hydrochloride respectively, in theprocedure described in Example 9, part B above, there is obtained as theproduct l-imino-4-chloro-3-(2-n-hexylamino-4-imino-2-thiazolin-5-ylidene)isoindoline hydrochloride.

B. Following the procedure described in Example 8 above but using anequivalent amount of l-imino-4- chloro-3-(Z-n-hexylamino-4-imino-2-thiazolin-5- ylidene)isoindoline in thefree-base form in place of limino-3-( 2,4-diimino-5 -thiazolidinylidene)isoindoline, there is obtained as the product a metal chelate pigmentcorresponding to Formula III in which Me is Co; R is Cl; R, R, and R areeach hydrogen; N=B is NH-n- C,,H,;,', and An is Cl.

EXAMPLE IS A. When equivalent amounts of 4,5-dimethyll ,3-diiminoisoindoline and 2-anilino-4-imino-2-thiazoline hydrochloride aresubstituted for the l,3-diiminoisoindoline andZ-piperidiono-4-imino-2-thiazoline hydrochloride respectively, in theprocedure described in Example 9, part B above, there is obtained as theproduct l -imino-4,5-dimethyl-3 2-anilino-4-imino- 2-thiazolin-5-ylidene )isoindoline hydrochloride.

B. Following the procedure described in Example 9. part C above butusing equivalent amounts of l-imino- 4,S-dimethyl-3-(2-anilino-4-imino2-thizolin-5- ylidene )isoindoline in the free-baseform and nickel (ll) bromide trihydrate in place of l-imino-3-(2-piperidino-4-imino-2-thiazolin-5-ylidene)isoindoline and nickel (ll)chloride hexahydrate respectively, there is obtained as the product ametal chelate pigment corresponding to Formula lll in which Me is Ni; Rand R are each CH R and R, are each hydrogen; N=B is NHC H and An is Br.

EXAMPLE 19 A. When an equivalent amount of S-bromo-l,3-diiminoisoindoline is substituted for the 1,3- diiminoisoindoline in theprocedure described in Example 4, part A above, there is obtained as theproduct l-imino-5-brorno-3-( 2-oxo-4-imino-5- thiazolidinylidene)isoindoline.

B. Following the procedure described in Example 4, part B above butusing an equivalent amount of limino-S-bromo- 3-( 2-oxo-4-imino-5-thiazolidinylidene)isoindoline in place of l-imino-3-( 2-0xo-4-imino-S-thiazolidinylidene)isoindoline, there is obtained as theproduct a metal chelate pigment correspnding to Formula [I in which Meis Ni; R is Br; R. R, and R are each hydrogen; Z is O; and An is OH.

EXAMPLE A. Following the procedure described in Example 9, part B abovebut using equivalent amounts of 5,6-diiodo-4,7-dimethoxy-l,3-diiminoisoindoline and2-diethylamino-4-imino-2-thiazoline hydrochloride in place ofl,3-diiminoisoindoline and 2-piperidino-4-imino-2- thiazolinehydrochloride respectively, there is obtained as the productl-imino-5,6-diiodo-4,7-dimethoxy-3-(2- diethylamino-4-imino-2-thiazolin-S-ylidene )isoindoline hydrochloride.

B. When an equivalent amount of l-imino-i-diiodo-4,7-dimethoxy-3-(2-diethylamino-4-imino-2- thiazolin-S-ylidene)isoindoline in the form ofthe freebase is substituted for the l-imino-3-(2-piperidino-4-imino-2-thiazolin-5 ylidene)isoindoline in the procedure described inExample 9, part C above, there is obtained as the product a metalchelate pigment corresponding to Formula Ill in which Me is Ni; R and R;are each OCH R, and R are each I; N=B is N(C H and An is Cl.

EXAMPLE 2] A. When the procedure described in Example 9, part B above isfollowed but using equivalent amounts of4,5,6,7-tetrabromo-l,3-diiminoisoindoline and Z-N-methylethylarnino-4-imino-2-thiazoline hydrochloride in place of the1,3-diiminoisoindoline and Z-piperidino- 4-imino-2-thiazolinehydrochloride respectively, there is obtained as the productl-imino-4,5,o,7-tetrabromo- 3-(2-N-methylethylamino-4-imino-Z-thiazolin-S- ylidene)isoindolinehydrochloride.

B. Following the procedure described in Example 7 above but using anequivalent amount of l-imino-4,5,6,7-tetrabromo-3-(2-N-methylethylamino-4-imino-Z-thiazolin-S-ylidene)isoindoline in the free-base form in place ofl-imino-3-( 2,4-diimino-5- thiazolidinylidene)isoindoline, there isobtained as the product a metal chelate pigment corresponding to FormulaIII in which Me is Cu; R, R,, R and R are each Br; N=B is N(CH )C H andAn is Cl.

EXAMPLE 22 A. When equivalent amounts of 5-chloro-4,5,6,7-tetrahydro-l,3-diiminoisoindoline and Z-di-t-butylamino- 4-imino-2-thiazolinehydrochloride are substituted for the l,3-diiminoisoindoline and2-piperidino-4-imino-2- thiazoline hydrochloride respectively, in theprocedure described in Example 9, part B above, there is obtained as theproduct 1-imino-5-chloro-4,5,6,7-tetrahydro-3-(Z-di-t-butylamino-4-imino-Z-thiazolin-S ylidene)isoindolinehydrochloride.

B. Following the procedure described above in Example 8 but substitutingan equivalent amount oflimino-5-chloro-4,5,6,7-tetrahydro-3-(Z-di-tbutylamino-4-imino-2-thiazolin-S-ylidene)isoindoline in the free-base form or the l-imino-3-( 2,4-diimino-5-thiazolidinylidene)isoindoline used in that examle, there is obtainedthe metal chelate pigment which correponds to Formula V in which Me isCo; R is Cl; R, R, and R are each hydrogen; N=B is N(t-C.,H,,) and An isCl.

EXAMPLE 23 A. When equivalent amounts of S-phenyl-l ,3-diiminoisoindoline and Z-di-n-hexylamino-4-imino-2- thiazolinehydrochloride are substituted for the 1,3- diiminoisoindoline and2-piperidino-4 imino-Z-thiazoline hydrochloride respectively, in theprocedure described in Example 9, part B above, there is obtained as theproduct l-imino-5-phenyl-3-(2-di-n-hexylamino-4-imino-2-thiazolin-5-ylidene )isoindoline hydrochloride.

B. Following the procedure described in Example 9, part C above butusing an equivalent amount oflimino-5-phenyl-3-(2-di-n-hexylamino-4-imino-2-thiazolin-S-ylidene)isoindoline in the form of the free base in place of1-imino-3-( 2-piperidino-4-imino-2- thiazolin-5-ylidene)isoindoline,there is obtained as the product a metal chelate pigment correspondingto Formula ill in which Me is Ni; R is C H R, R, and R are eachhydrogen; N=B is N(n-C,,H, and An is Cl.

EXAMPLE 24 A. Proceeding in a manner similar to that described above inExample 3, part A but substituting an equivalent amount of4,7-difluoro-l,3-diiminoisoindoline for thel,3-diimino-4,5,6,7-tetrach1oroisoindoline used in that example, thereis obtained l-imino-4,7-difluoro-3-(2,4-diimino-5-thiazolidinylidene)isoindoline acetate.

B. When an equivalent amount of l-imino-4,7 difluoro-3 2,4-diimino-5-thiazolidinylidene )isoindoline acetate is substituted forthe l-imino-4,5,6,7-tetrachloro-3-( 2,4-diimino-5 -thiazolidinylidene)isoindoline acetate in the procedure described in Example 3, part Babove, there is obtained as the product a metal chelate pigmentcorresponding to Formula II in which Me is Ni; Z is NH; R and R are eachF; R, and R are each hydrogen; and An is C].

EXAMPLE 25 A. Using a procedure similar to that described in Example 9,part B above but substituting 4-methyl-5,6,7- triphenyll,3-diiminoisoindoline and 2-benzylamino-4- imino-2-thiazolinehydrochloride for the l,3- diiminoisoindoline and2-pipen'dino-4-imino-2-thiazoline hydrochloride respectively, there isobtained as the product l-imino-4-methyl-5 ,6,7-triphenyl-3-(Z-benzylamino-4-imino-2-thiazolin-5-ylidene)isoindoline hy drochloride.

B. Following the procedure described in Example 9, part C above butusing an equivalent amount oflimino-4-methyl-5,6,7-triphenyl-3-(2-benzylamino-4-imino-Z-thiazoline-S-ylidene)isoindoline in the freebase form in placeof l-imino-3-(2-piperidino-4-imino- Z-thiazolin-S-ylidene)isoindoline.there is obtained as the product a metal chelate pigment correspondingto Formula III in which Me is Ni; R, R, and R are each C H R is CH N=Bis NH-CH- -C H and An is Cl EXAMPLE 26 A. When equivalent amounts of5,6-dimethoxy- 4,5,6,7,-tetrahydro-l,3-diiminoisoindoline and 2-(3-phenylpropylamino)-4-imino-2-thiazoline hydrochloride are substitutedfor the 4.5,6,7-tetrahydro l,3- diiminoisoindoline and2,4-diiminothiazolidine hydrochloride respectively, in the proceduredescribed in Example 10, part A above, there is obtained as the productl-imino-5,6-dimethoxy-4,5,6,7-tetrahydro-3-[2-(3- phenylpropylamino )-4imino-Z-thiazolin-S- ylidenehsoindoline.

B. By substituting an equivalent amount of l-imino- S ,6-dimethoxy-4.5,6,7-tetrahydro-3-[ 2-(3-phenylpropylamino)-4-imino-2-thiazolin-S-ylidenelisoindoline for thel-imino-3-( 2,4-diimino-5- thiazolidinylidene)isoindoline in theprocedure described in Example 7 above, there is obtained the metal 25chelate pigment represented by Formula V above wherein Me is Cu; R, andR are each OCH R and R are each hydrogen; N=B is NH-(Cl-l -C,,H,,; andAn is Cl.

EXAMPLE 27 A. Following the procedure described in Example 9. part Babove but using equivalent amounts of 5,6 dichloro-l,3-diiminoisoindoline and Z-(S-phenylpentylamino)-4-imino-2-thiazolinehydrochloride in piaee of the l,3-diiminoisoindoline and 2-piperidino-4-imino-2-thiazoline hydrochloride respectively, there is obtained as theproduct l-imino-5,6-dichloro-3-[2-(5-phenylpentylamino)-4-imino-2-thiazolin-5- ylidenelisoindolinehydrochloride.

B. When an equivalent amount of l-imino-5,6- dichloro-3-[ 2-(S-phenylpentylamino )-4-imino-2- thiazolin-S-ylidene]-isoindoline in theform of the free base is substituted for the l-imino-3-(2-piperidino-4-imino-2 thiazolin--ylidene)isoindoline in the procedure described inExample 9, part C above, there is obtained as the product a metalchelate pigment corresponding to Formula [II in which Me is Ni; R, and Rare each Cl; R and R are each hydrogen; N=B is NH- (CH2)5"C6H5; and AnlS CL EXAMPLE 28 A. Following a procedure similar to that described inExample 4, part A above but substituting equivalent amounts of5,6-dimethyl-4,5,6,7-tetrahydro- 1,3- diiminoisoindoline and4-imino-2-thiazolidenethione for the 1,3-diiminoisoindoline and4-imino-2-thia1olidinone respectively, there is obtained as the product1- imino-S,6-dimethyl-4,5,6,7-tetrahydro-3-(2-thioxo-4-imino-S-thiazolidinylidene )isoindoline.

B. When an equivalent amount of l-imino-5,6-diemthyl-4.5,6,7-tetrahydro-3-( 2-thioxo-4-imino-5-thiazolidinylidene)isoindoline is substituted for the limino-3-(2,4-diimino-5-thiazolidinylidene)isoindoline in the procedure describedin Example 7 above, there is obtained as the product a metal chelatepigment corresponding to Formula IV in which Me is Cu; R, and R are eachCH R and R are each hydrogen; 2 is S; and An is Cl.

EXAMPLE 29 A. Following the procedure described in Example 9, part Babove but equivalent amounts of 4,7-diethoxyl,3-diiminoisoindoline andZ-N-ethylanilino-4-imino-2- thiazoline hydrochloride in place ofl,3-diiminoisoindoline and 2-piperidino-4-imino-2-thiazolinehydrochloride respectively, there is obtained as the product I-imino-4,7-diethoxy-3-( 2-N-ethylanilino-4-imino-2-thiazolin-5-ylidene)isoindoline hydrochloride.

B. When an equivalent amount of l-imino-4,7-diethoxy-3-(2-N-ethylanilino-4-imino2-thiazolin-5- ylidene)isoindoline in the formof the free base is substituted for l-imino-3-( 2,4-diimino-5-thiazolidinylidene)isoindoline in the procedure described in Example 7above, the product obtained is a metal chelate pigment corresponding toFormula ill in which Me is Cu; R and R are each OC H R, and R are eachhydrogen; N=B is N(C H )C,,H and An is Cl.

EXAM PLE 30 A. Employing a procedure similar to that described inExample l0, part A above. but substituting equivalent amounts of5-methyl-4-phenyl-4,5,6,7-tetrahydrol,3-diiminoisoindoline and2-N-butylanilino-4-imino- Z-thiazoline hydrochloride for4,5,6,7-tetrahydro-l ,3- diiminoisoindoline and 2,4-diiminothiazolidinehydrochloride respectively, there is obtained as the product l-imino-S-methyl-4-phenyl-4,5,,7-tetrahydro- 3-( 2-N-butylanilino-4-imino-2-thiazolii.-5-ylidene)isoindoline hydrochloride.

B. When an equivalent amount of l-imino-S-methyl-4-phenyl-4,5,6,7-tetrahydro-3-(2-N-butylanilino4-imino-2-thiazolin-5-ylidene)isoindoline in the free-base form issubstituted for the l-imino-4,5,6,7-tetrahydro-3-(2,4-diimino-5-thiazolidinylidene)isoindoline in the proceduredescribed in Example 10, part B above, there is obtained as the productas a metal chelate pigment corresponding to Formula V in which Me is Ni;R and R are each hydrogen R is methyl; R is phenyl; N=B is N(C,H )C,;Hand An is Cl.

EXAMPLE 31 A. Proceeding in a manner similar to that described above inExample 10, part A but substituting equivalent amounts of4-(p-chlorophenyl)-4,5,6,7-tetrahydrol ,3-diiminoisoindoline and 2-(p-ethylanilino)-4- imino-2-thiazoline hydrochloride for4,5,6,7-tetrahydro-l ,3-diiminoisoindoline and 2,4-diiminothiazolidinehydrochloride, there is obtained as the product I- imino-4-(p-chlorophenyl )-4,5 ,6,7-tetrahydro-3-[ 2-(pethylanilinol-4-imino-2-thiazolin-5-ylidene]isoindoline.

B. Following the procedure described in Example 10, part B above butusing an equivalent amount of limino-4-( p-chlorophenyl )-4,5,6,7-tetrahydro-3-[ 2-(pethylanilino)-4-imino-2-thiazolin-5-ylidenelisoindoline in place of thel-imino-4,5,6,7-tetrahydro-3-(2,4-diimino-S-thiazolidinylidene)isoindoline, there is obtained as theproduct a metal chelate pigment corresponding to Formula V in which Meis Ni; R is p- (Cl )C,,-H.,; R, R, and R are each hydrogen; N=B isNl-lp-(C,H )C,,H,: and An is Cl.

EXAMPLE 32 A. When equivalent amounts of 5-(2,4,Strimethylphenyl)-l,3-diiminoisolindoline and Z-dibenzylamino- 4-imino-2-thiazolinehydrochloride are substituted for the l ,3 -diiminoisoindoline and2-piperidino-4-imino-2- thiazoline hydrochloride in the proceduredescribed in Example 9, part B above, there is obtained as the productl-imino-5-( 2,4,5-trimethylphenyl )-3-( 2-dibenzylamino-4-imino-Z-thiazolin-S-ylidene)isoindoline hydrochloride.

B. Following the procedure described in Example 9, part C above, butusing an equivalent amount of limino-5-( 2,4,5-trimethylphenyl )-3-(2-dibenzylamino- 4-imino-2-thiazolin-S-ylidene)isoindoline in thefreebase form in place of l-imino-3-(2-piperidino-4-imino-2-thiazolin-5-ylidene)isoindoline, there is obtained as the product ametal chelate pigment corresponding to Formula III in which Me is Ni; Ris 2,4,5-(CH -C,,H R, R, and R are each hydrogen; N=B is N-(CH C fl h;and An is Cl.

EXAMPLE 33 A. Proceeding in a manner similar to that described above inExample 4, part A. but substituting an equivalent amount of S-ethoxyl,3-diiminoisoindolinc for L3- diiminoisoindoline, there is obtained asthe product I- imino-5-ethoxy-3-( 2-oxo-4-imino-5-thiazolidinylidene)isoindoline.

B. When an equivalent amount of l-imino-S-ethoxy- 3-(2-oxo-4-imino-S-thiazolidinylidene )isoindoline is substituted for l-imino-3-( 2,4-diimino-- thiazolidinylidene)isoindoline in the proceduredescribed in Example 8 above, there is obtained as the product a metalchelate pigment corresponding to Formula II in which Me is Co; R is OC HR, R, and R are each hydrogen; Z is O; and An is Cl.

EXAMPLE 34 A. Following the procedure described in Example 9, part Babove, but using equivalent amounts of 7-ethoxy-4-methyl-5-phenyl-1,3-diiminoisoindoline and2-N-ethylbenzylamino-4-imino-Z-thiazoline hydrochloride in place of1,3-diiminoisindoline and 2-piperidino- 4-imino-2-thiazolinehydrochloride respectively, there is obtained as the productl-imino-7-ethoxy-4-methyl- 5-phenyl-3-(2-N-ethylbenzylamino-4-imino-2-thiazolin-S-ylidene )isoindolinehydrochloride.

B. When equivalent amounts of l-imino-7-ethoxy-4- methyl-5-pheny1-3-(2-N-ethylbenzylamino-4-imino-2- thiazolin-S-ylidene)isoindoline in theform of the free base and nickel (ll) bromide trihydrate are substitutedfor the l-imino-3-(Z-piperidino-4-imino-2thiazolin-5-ylidineJisoindoline and nickel (ll) chloride hexahydrate respectively,in the procedure described in Example 9, part C above, there is obtainedas the product a metal chelate pigment corresponding to Formula [II inwhich Me is Ni; R is OC H R, is hydrogen; R is C H R is CH N=B is N(C H)CH C,,-H and An is Br.

EXAMPLE 35 A. Employing a procedure similar to that described in Example9, part B above, but substituting equivalent amounts of4,5,7-trimethyl-l,3-diiminoisoindoline and2-(p-chloroanilino)-4-imino-2-thiazoline hydrochloride for1,3-diiminoisoindoline and 2-piperidino-4- imino-2-thiazolinehydrochloride respectively, there is obtained as the productl-imino-4,5,7-trimethyl-3-[2-(p-chloroanilino)-4-imino-Z-thiazolin-S-ylidenelisoindolinehydrochloride.

B. Following the procedure described in Example 9, part C above butusing an equivalent amount of 1- imino-4,5 ,7-trin1ethyl-3-Z-(p-chloroanilino )-4-imino- Z-thiazolin-S-ylidene]isoindoline in thefree-base form in place ofl-imino-3-(2-piperidino-4-in1ino-2-thiazolin-S-ylidene )isoindoline,there is obtained as the product a metal chelate pigment correspondingto Formula [II in which Me is Ni; R, R and R are each CH R, is hydrogen;N=B is Nl-l-p-ClC H,; and An is Cl.

EXAMPLE 36 A. When equivalent amounts of4-(3,4-dimethoxyphenyl)-4,5,6,7-tetrahydrol ,3-diiminoisoindoline and2-(o-methoxyanilino)-4-imino-2-thiazoline hydrochloride are substitutedfor the 4,5,6,7-tetrahydrol,3- diiminoisoindoline and2,4-diiminothiazolidine hydrochloride respectively, in the proceduredescribed in Example lO, part A above, there is obtained as the productl-imino-4-( 3,4-dimethoxyphenyl )-4 ,5 ,6,7-tetrahydro-3-[ 2-(o-methoxyanilino )-4-imino-2-thiazolin- 5- ylidene isoindolinehydrochloride.

B. Following the procedure described in Example l0, part B above, butusing an equivalent amount of limino-4-( 3,4-dimethoxyphenyl )-4,5,6,7-tetrahydro-3- [2-(o-methoxyanilino)-4-imino-2-thiazolin-5-ylidenelisoindoline hydrochloride in place of l-imino-4,5,6,7-tetrahydro-3-( 2,4-diimino-5- 28 thiazolidinylidene)isoindoline,there is obtained as the product a metal chelate pigment correspondingto Formula V in which Me is Ni; R is 3,4(OCH C H R, R, and R are eachhydrogen; N=B is NHo- (OCH- ,)C,,H,; and An is Cl.

EXAMPLE 37 A. Following the procedure described in Example 10, part Aabove, but using equivalent amounts of 4,5,7-triphenyl-4,5,6,7-tetrahydro-l ,3-diiminoisoindoline and2-N-methyl(p-bromobenzylamino)-4-imino-2- thiazoline hydrochloride inplace of 4,5,6,7-tetrahydro- 1,3-diiminoisoindoline and2,4-diiminothia2olidine hydrochloride respectively, there is obtained asthe product of l-imino-4,5,7-triphenyl-4,5,6,7-tetrahyclro-3-[2-N-methyl(p-bromobenzylamino)-4-imino-2-thiazolin- S-ylidenelisoindoline.

B. When an equivalent amount of l-imino-4,5,7- triphenyl-4,5,6,7-tetrahydro-3-[ 2-N-methyl(pbromobenzylamino)-4-imino-2-thiazolin-5- ylidenelisoindoline issubstituted for the l-imino-3-(2-oxo-4-imino-S-thiazolindinylidene)isoindoline in the procedure describedabove in Example 4, part B, there is obtained as the product a metalchelate pigment corresponding to Formula V in which Me is Ni; R, R and Rare each C H R, is hydrogen; N=B is N(CH )-pBrC,,H,,Cl-l and An is CH.

EXAMPLE 38 A. Proceeding in a manner similar to that described above inExample 3, part A, but substituting an equivalent amount of5,6-dibromo-4,7-difluorol ,3- diiminoisoindoline for l-3 ,diimino-4,5,6,7-tetrachloroisoindoline, there is obtained as the product 1-imino-S,6-dibromo-4,7-difiuoro-3-( 2,4-diimino-5- thiazolidinylidene)isoin doline acetate.

B. Following the procedure described in Example 3, part B above, butusing an equivalent amount of limino-S ,6-dibromo-4,7-difluoro-3-( 2,4-diimino-S- thiazolidinylidene)isoindoline in the free-base form inplace of l-imino-4,5,6,7-tetrachloro-3-(2,4-diimino-5-thiazolidinylidene)isoindoline, there is obtained as the product a metalchelate pigment corresponding to Formula [I in which Me is Ni; R and Rare each F; R, and R are each Br; Z is NH; and An is Cl.

EXAMPLE 39 A. When equivalent amounts of 4-(p-bromophenyl)- 7-phenyl-4,5,6,7-tetrahydrol ,3-diiminoisoindoline and2-pyrrolidino-4-imino-2-thiazoline hydrochloride are substituted for the4,S,6,7-tetrahydro-l ,3- diiminoisoindoline and 2,4-diiminothiazolidinehydrochloride respectively, in the procedure described in Example lO,part A above, there is obtained as the product l-imino-4-( p-bromophenyl)-7-phenyl-4,5,6,7-tetrahydro-3-( Z-pyrrolidino-4-imino-2-thiazolin-S-ylidene)isoindoline.

B. Following the procedure described in Example 10, part B above butusing an equivalent amount of limino-4-( p-bromophen yl )-7-phenyl-4 ,5,6,7-tetrahydro-3-(2-pyrrolidino-4-imino-Z-thiazolin-S-ylidene)isoindoline in place of l-imino-4,5,6,7-tetrahydro- 3-(2,4-diimino-5 -thiazolidinylidene )isoindoline there is obtained as theproduct a metal chelate pigment corresponding to Formula V in which Meis Ni; R is C,,H R is p-BrC,,H,; R, and R are each hydrogen; N=B ispyrrolidino; and An is Cl.

EXAMPLE 40 A. When an equivalent amount of 4-isopropyl-7-methyl-l,Bdiiminoisoindoline is substituted for L3- diiminoisoindolinein the procedure described in Example 9, part B above, there is obtainedas the product l-imino-4-isopropyl-7-methyl-3-( 2-piperidino-4-imino-2-thiazolin-5-ylidene)isoindoline hydrochloride.

B. Following the procedure described in Example 9, part C above, butusing an equivalent amount of limino-4-isopropyl-7-methyl-3-(2-piperidino-4-imino-2- thiazolin--ylidene)isi)indoline in the form ofits free base in place of l-imino-3-(2-piperidino-4-imino-2-thiazolin-S-ylidene )isoin L: iline, there is obtained as the product ametal chelate pigment corresponding to Formula III in which Me is Ni", Ris CH R and R are each hydrogen; R is iSO-CgHg; N=B is piperidino; andAn is Cl.

EXAMPLE 41 A. Proceeding in a manner similar to that described inExample 9, part B above, but substituting 4,5-dipropyl-7-ethoxyl,3-diiminoisoindoline and Z-morpholino-4-imino-2-thiazolinehydrochloride in equivalent amounts for 1,3-diiminoisoindoline and 2-piperidino-4-imino-2-thiazoline hydrochloride respectively, there isobtained as the product l-imino-4,5- dipropyl-7-e thoxy-3-(2-morpholino-4imino-Z-thiazo- Iin-S-ylidene )isoindoline hydrochloride.

B. When an equivalent amount of l-imino-4,5-dipropyl-7-ethoxy-3-(2-morpholino-4-imino-2 thiazolin-5- ylidene)isoindoline in the free-baseform is substituted for l -imino-3-( 2-piperidino-4-imino-2-thiazolin-5- ylidene)isoindoline in the proceduredescribed in Example 9, part C above, there is obtained as the product ametal chelate pigment corresponding to Formula ill in which Me is Ni; Ris OC H R is hydrogen; R and R are each C H N=B is morpholino; and An isCl.

EXAMPLE 42 A. Following the procedure described in Example 9, part Babove but using equivalent amounts of 5-chloro- 4,6,7-trifluoro-l,3-diiminoisoindoline and 2-( Z-methylpiperidino)4-imino-2-thiazolinehydrochloride in place of 1,3-diiminoisoindoline and 2-piperidino-4-imino-Z-thiazoline hydrochloride respectively, there is obtained as theproduct l-imino-5-chloro-4,6,7-trifluoro-3- 2-( Z-methylpipe ridino)-4-imino-2-thiazolin- 5-ylidene]isoindoline hydrochloride.

B. When an equivalent amount of l-imino-5-chloro- 4,6,7-trifluo ro-3-[2-( Z-rnethylpiperidino )-4-imino-2- thiazolin-S-ylidenelisoindoline inits free-base form is substituted for the1-imino-3-(2-piperidino-4-imino-2- thiazolin-S-ylidene)isoindoline, inthe procedure described in Example 9, part C above, there is obtained asthe product a metal chelate pigment corresponding to Formula Ill inwhich Me is Ni; R, R and R are each F; R is Cl; N=B is 2-(CH )C l-l N;and An is Cl.

EXAMPLE 43 A. When equivalent amounts4,5,74,5,7-trimethoxyl,3-diiminoisoindoline and 2-(3-ethylpyrrolidino)-4- imino-Z-thiazoline hydrochloride are substitutedfor the l,3-diiminoisoindoline and 2-piperidino-4-imino-2- thiazolinehydrochloride respectively, in the procedure described in Example 9,part C above, there is obtained as the productl-imino-4,5,6-trimethoxy-3-[2-(3-ethyl- 30pyrrolidino)-4-imino-Z-thiazolin-S-ylidene]isoindoline hydrochloride.

B. Following the procedure described in Example 9, part C above butusing an equivalent amount of limino-4,5 ,7trimethoxy-3-[ 2-(3-ethylpyrrolidino )-4- imino-Z-thiazolin-S-ylidenelisoindoline in itsfree-base form in place of l-imino-3-(2-piperidino-4-imino-2-thiazolin-S-ylidene)isoindoline, there is obtained as the product ametal chelate pigment corresponding to Formula [II in which Me is Ni; R,R and R are each OCH R, is hydrogen; N=B is 2-(C H )C H N; and An is C].

EXAMPLE 44 A. Proceeding in a manner similar to that described above inExample 10, part A, but substituting equivalent amounts of4-bromo-6-methyl-4,5,6,7-tetrahydro- 1,3-diiminoisoindoline and 2-(3-methylmorpholino)-4- imino-2-thiazoline hydrochloride for4,5,6,7-tetrahydrol ,3-diiminoisoindoline and 2,4-diiminothiazolidinehydrochloride respectively, there is obtained as the productl-imino-4-bromo-6-methyl-4 ,5 ,6, 7-tetrahydro-3-[ 2-(3-methylmorpholino )-4-imino-2-thiazolin -5- ylidene]isoindoline.

B. When an equivalent amount of l-imino-4-bromo- 6-methyl-4,5,6,7-tetrahydro-3-[2-(3-methylmorpholino)-4-imino-2-thiazolin-5-ylidene]isoindoline issubstituted for 1-imino-4,5,6,7-tetrahydro-3-(2,4-diimino-S-thiazolidinylidene)isoindoline in the procedure described inExample l0, part B above, there is obtained as the product a metalchelate pigment corresponding to Formula V in which Me is Ni; R is CH Ris Br; R and R are each hydrogen; N=B is 2- (CH )C H NO; and An is Cl.

EXAMPLE 45 A. When an equivalent amount of4,5,6,7-tetraphenyl-l,3-diiminoisoindoline is substituted for the L3-diimino-4,5,6,7-tetrachloroisoindoline in the procedure described inExample 3, part A above, there is obtained as the productl-imino-4,5,6,7-tetraphenyl-3- (2,4-diimino-5-thiazolidinylidene)isoindoline acetate.

B. Following the procedure described in Example 3, part B above butusing an equivalent amount oflimino-4,5,6,7-tetraphenyl-3-(2,4-diimino-5-thiazolidinylidene)isoindoline acetate in place oflimino-4,5,6,7-tetrachloro-3-(2,4-diimino-5-thiazolidinylidene)isoindoline acetate, there is obtained as the producta metal chelate pigment corresponding to Formula [I in which Me is Ni;R, R,, R and R are each C H Z is NH; and An is Cl.

EXAMPLE 46 This example is representative of one of the proceduresemployed for the evaluation of the novel pigments of this invention ascoloring agents for coating compositions.

A mixture of two parts of the novel pigment obtained in Example 1, partC above, seven parts of an acrylic resin, four parts of xylol and 20parts of l/ l 6 inch diameter steel balls was charged into a containerwhich was placed in a mechanical shaker. Shaking was effected for 1hour. The container was removed from the shaker and to the mixture therewas added an additional 17 parts of the acrylic resin and an additionalten parts of xylol. The container was again placed in the shaker andshaking was effected for fifteen minutes longer. The steel balls wereremoved from the mixture and portions of the composition, whichcontained approximately exposure, there was no observable loss instrength or shade.

EXAMPLE 47 The novel pigments of this invention were evaluated for usein preparing coating compositions suitable for outdoor exposure, such asautomobile finishes. Representative of the method employed is thefollowing description of the preparation and testing of a metallic"automobile finish.

A pigment base was prepared by subjecting a mixture of l5.7 parts of thechelate pigment from Example I, part C above, and 16.2 parts of acrylicresin dissolved in 24.6 parts of xylol to attrition in a steel ball mill/2 inch balls) for 48 hours. To the milled mixture there was then addedan additional 4.3 parts of acrylic resin dissolved in 26.2 parts ofxylol. The pigment base, which contained 18 percent pigment wasincorporated in a coating composition containing 7.7 parts of thepigment base, 3.3 parts of a 30 percent aluminum paste, 19.5 parts ofacrylic resin, 15.2 parts of a melamine resin, l.3 parts of butanol and35 parts of xylol. The resultant composition was sprayed onto primed 4 X12 inch steel test panels and the coated panels were then placed in acuring oven at 300F for 30 minutes. There was thus produced a pleasingblue-red transpan ent and glossy metallic finish on the test panels.

The coated panels were then tested by outdoor exposure in Flordia andunder desert sun in Arizona. After l2 months of this continuous exposurethere was essentially no perceptible change in the hue, brightness andstrength of the pigment.

We claim: 1. A metal chelate pigment of the formula in which zero to twoof R, R R and R are alkyl having 1 to 3 carbon atoms, alkoxy having 1 to3 carbon atoms or phenyl, or are otherwise hydrogen; 0 to 4 of R, R,, Rand R are chlorine or are otherwise hydrogen; and An is a solublecolorless anion.

2. The metal chelate pigment of the formula in which An is a solublecolorless anion.

Page 1 of 4 UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OFCORRECTION PATENT N0. 3,919,235

DATED 1 November 11, 1975 INVENTOMS) 3 Nathan N. Crounse and Nicholas A.Ambrosiano It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 23, the part of the structure which reads ME should readMe C- C-NH Column 2, line 40, the central part of the structure whichreads N should read N r r t t N N N N M Me Column 3, line 9, the part ofthe structure which reads 0 H C --N L N-- C should read Me U C--(\Z-NHHN=C\Z-C S S \C:==N1 N-(:/ lkB N=B C N N-C H 7 I S c II=NH NH= 'I c s\C=N N=C/ N=B II C:

Page 2 of 4 UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OFCORRECTION PATENT N0.

DATED are hereby corrected as shown below:

November ll,

INVENTOMS) 3 Nathan N. Crounse and Nicholas A. Ambrosiano It iscertified that error appears in the above-identified patent and thatsaid Letters Patent line 64, the part of the structure which readsColumn 6, line 44, "ylideneisoindolines" should read Column 3, =NH"should read C-NH ylidene)isoindolines Column 9, line 61, "preparationshould read preparative Column 10, line Column 10, hereinabove lineColumn ll, line thiazolidinylidene Column 11, thiazolin line Column 11,line thiazolidinylidene Column ll, line toluenesul Column 12, linethiazolidinylidene Column 12, line Column 12, line "thiazolidinylindene"should read "7ethoxy" should read 7-ethoxy --J "ethoxy" should readEthoxy Page 3 of 4 PATENT NO.

DATED INVENTOR(S) I 3 November 11,

Nathan N. Crounse and Nicholas A. Ambrosiano It is certified that errorappears in the ab0ve-identified patent and that said Letters Patent arehereby corrected as shown below:

Column 12,

line 59, "Bdiiminoisoindoline" should read B-diiminoisoindoline Column12, line 60, "chloro" should read Chloro Column 12, line 64, "(c3)"should read (3) Column 13, line 6, "diiminoisoindoline" should readdiiminoisoindoline (3) Column 13, line 14, start "4-(p-Bromophenyl)..."on new line.

Column 13, lines 18 and 19 should be deleted.

Column 15, line 18, "n" should read N Column 32, Claim 1, lines l-2lshou1d read R --R R --R2 2x I P c cn C L l l I. K ll 2 H /C---C:NHHN=C---C\ S\ i /q I cl w w. t C)

1. A METAL CHELATE PIGMENT OF THE FORMULA
 2. The metal chelate pigmentof the formula